Abstract:

Disclosed is a composition comprising: an aqueous dispersion of
fluoroalkylsilyl surface modified nanoparticles, wherein the
nanoparticles comprise at least one member selected from the group
consisting of silica, titania, zirconia, layered magnesium silicate,
aluminosilicate, natural clay, synthetic clay and mixtures thereof, and
wherein the fluoroalkylsilyl is:
(F(CF2)nCH2CH2)mSi(O--)p, where n is 2, 3
or 4, p is 1, 2 or 3, and m is (4-p). Also disclosed are processes of
making an aqueous dispersion of fluoroalkylsilyl surface modified
nanoparticles, and treating a substrate with an aqueous dispersion of
fluoroalkylsilyl surface modified nanoparticles. Articles and substrates
comprising the fluoroalkylsilyl surface modified nanoparticles are also
disclosed.

Claims:

1. A composition comprising an aqueous dispersion of fluoroalkylsilyl
surface modified nanoparticles, wherein the nanoparticles comprise at
least one member selected from the group consisting of silica, titania,
zirconia, layered magnesium silicate, aluminosilicate, natural clay,
synthetic clay and mixtures thereof, and wherein the fluoroalkylsilyl
is:(F(CF2)nCH2CH2)mSi(O--)p,where n is 2, 3
or 4,where p is 1, 2 or 3, andwhere m is (4-p).

2. The composition of claim 1 wherein n is 4.

3. The composition of claim 1 wherein p is 3 and m is 1.

4. The composition of claim 1 wherein the synthetic clay is hectorite
clay.

5. The composition of claim 1 wherein the fluoroalkylsilyl is covalently
bonded to the nanoparticle surface.

6. The composition of claim 1 wherein the fluoroalkylsilyl surface
modified nanoparticle is present at a concentration in the range of from
about 0.01% to about 50% by weight of the total composition.

7. The composition of claim 1 wherein the fluoroalkylsilyl surface
modified nanoparticle is present at a concentration in the range of from
about 1% to about 40% by weight of the total composition.

8. The composition of claim 1 wherein the fluoroalkylsilyl surface
modified nanoparticle is present at a concentration in the range of from
about 1% to about 8% by weight of the total composition.

9. The composition of any of claims 1-9 further comprising a fluorinated
resin emulsion.

10. The composition of any of claims 1-9 further comprising an alkylated
inorganic nanoparticle having no fluorine.

11. The composition of any of claims 1-9 further comprising at least one
member selected from the group consisting of a wetting agent, anti-soil
agent, anti-stain agent, fluorochemical resin, surfactant and mixtures
thereof.

12. The composition of any of claims 1-8 further comprising a component
moiety bonded to the surface of the nanoparticles having the
formula:[H(CH2)M]nSi--(O--)p.where M is an integer
between 1 and 12,where p is 1, 2, or 3, andwhere n is 4-p.

13. A process for making fluoroaklysilyl surface modified nanoparticles,
comprising:(i) creating an aqueous dispersion of at least one member
selected from the group consisting of silica, titania, zirconia, layered
magnesium silicate, aluminosilicate, natural clay, synthetic clay and
mixtures thereof;(ii) adding a water immiscible fluoroalkylsilane reagent
to the aqueous dispersion to form a heterogeneous mixture where the
fluoroalkylsilane reagent
is:(F(CF2)nCH2CH2)mSi(O--R)p,where n is 2,
3 or 4,where p is 1, 2 or 3,where m is (4-p), andwhere R is selected from
the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl,
isobutyl, and --C(O)CH3; and(iii) mixing the heterogeneous mixture
until it becomes a homogeneous aqueous dispersion of fluoroaklysilyl
surface modified nanoparticles.

14. The process of claim 13 wherein n is 4, p is 3, m is 1, R is selected
from the group consisting of methyl and ethyl, and the synthetic clay is
a hectorite clay.

15. The process of claim 13 or 14 wherein the fluoroalkylsilane molecules
are covalently bonded to the nanoparticle surface, forming
fluoroalkylsilyl moiety on the surface of the nanoparticle.

16. The process of claim 13 or 14 wherein the fluoroalkylsilyl surface
modified nanoparticles are formed at a concentration in the range of from
about 0.01% to about 50% by weight of the aqueous dispersion.

17. The process of claim 13 or 14 wherein the fluoroalkylsilyl surface
modified nanoparticles are formed at a concentration in the range of from
about 1% to about 40% by weight of the aqueous dispersion.

18. The process of claim 13 or 14 wherein the fluoroalkylsilane surface
modified nanoparticles are formed at a concentration in the range of from
about 1% to about 8% by weight of the aqueous dispersion.

19. The process of claim 13 or 14 further comprising adding a fluorinated
resin emulsion.

20. The process of claim 13 or 14 further comprising adding an alkylated
inorganic nanoparticle having no fluorine.

21. The process of claim 13 or 14 further comprising adding at least one
member selected from the group consisting of a wetting agent, anti-soil
agent, anti-stain agent, fluorochemical resin, surfactant and mixtures
thereof.

22. The process of claim 13 or 14, further comprising adding a component
prior to the addition of the fluoroalkylsilane, wherein said component
has the formula:[H(CH2)M]n--Si--(X)p.where M is an
integer between 1 and 12,where p is 1, 2, or 3,where n is 4-p, andwhere X
is selected from the group consisting of methoxy, ethoxy, propoxy,
butoxy, acetoxy, and chloride leaving groups.

23. The process of claim 22, wherein said mixing further comprises
recirculating the fluoroalkylsilane and nanoparticles through a static
mixer.

24. A modified substrate comprising:a fluoroalkylsilyl surface modified
nanoparticle on at least one surface of said substrate, wherein the
nanoparticle comprises at least one member selected from the group
consisting of titania, zirconia, layered magnesium silicate,
aluminosilicate, natural clay, synthetic clay and mixtures thereof, and
wherein the fluoroalkylsilyl
is:(F(CF2)nCH2CH2)mSi(O--)p,where n is 2, 3
or 4,where p is 1, 2 or 3, andwhere m is (4-p)

25. The modified substrate of claim 24 wherein said substrate is selected
from the group consisting of synthetic fiber, natural fiber, stone,
ceramic, glass, plastic and composites.

26. The modified substrate of claim 24 wherein n is 4.

27. The modified substrate of claim 24 wherein p is 3 and m is 1.

28. The modified substrate of claim 27 wherein the synthetic clay is a
hectorite clay.

29. The modified substrate of claim 27 wherein the fluoroalkylsilyl is
covalently bonded to the nanoparticle surface.

30. The modified substrate of claim 24 or 25 wherein the substrate
comprises pores having an average diameter in the range of from about 100
to about 100,000 nanometers.

31. The modified substrate of claim 24 or 25 wherein the fluoroalkylsilyl
surface modified nanoparticle forms at least one layered structure on the
substrate, wherein the layered structure has a thickness of about 10,000
nanometers or less, and a width and length of about 100,000 nanometers or
more.

32. The modified substrate of claim 24, wherein the substrate further
comprises a component moiety bonded to the surface of the nanoparticle
having the formula:[H(CH2)M]n--Si--(O--)p.where M is
an integer between 1 and 12,where p is 1, 2, or 3, andwhere n is 4-p; and
further wherein said nanoparticle comprises at least one member selected
from the group consisting of silica, titania, zirconia, layered magnesium
silicate, aluminosilicate, natural clay, synthetic clay and mixtures
thereof.

33. An article made from the substrate of claim 24 or 32.

34. The article of claim 33 wherein the article is a fabric, carpet, or
paper.

35. The article of claim 34 wherein the article is a fabric or a carpet,
and further wherein said nanoparticle comprises at least one member
selected from the group consisting of silica, titania, zirconia, layered
magnesium silicate, aluminosilicate, natural clay, synthetic clay and
mixtures thereof.

36. The article of claim 35 wherein the total concentration of fluorine on
the external surface is in a range of from about 10 ppm to about 500 ppm
w/w.

37. The article of claim 35 wherein the total concentration of fluorine on
the external surface is in a range of from about 50 ppm to about 300 ppm
w/w.

38. The article of claim 35 wherein the fluoroalkylsilyl surface modified
nanoparticle is present from about 0.01% to about 2.0% by weight of the
article.

39. The article of claim 35 wherein the fluoroalkylsilyl surface modified
nanoparticle is present from about 0.1% to about 1.0% by weight of the
article.

40. The article of claim 35 wherein elemental fluorine is present from
about 0.0001% to about 0.10% by weight of the article.

41. The article of claim 35 wherein elemental fluorine is present from
about 0.0001% to about 0.010% by weight of the article.

42. The article of claim 35 wherein the fluoroalkylsilyl surface modified
nanoparticles is present from about 0.01 to about 3 grams per square
meter of surface area of the article.

43. The article of claim 35 wherein the fluoroalkylsilyl surface modified
nanoparticles is present from about 0.1 to about 2 grams per square meter
of surface area of the article.

44. A process for making a modified substrate that is hydrophobic and soil
resistant, comprising:(i) applying an aqueous dispersion of
fluoroalkylsilyl surface modified nanoparticles, wherein said
nanoparticles comprises at least one member selected from the group
consisting of silica, titania, zirconia, layered magnesium silicate,
aluminosilicate, natural clay, synthetic clay and mixtures thereof; and
wherein saidfluoroalkylsilyl is:
(F(CF2)nCH2CH2)mSi(O--)p,where n is 2, 3 or
4,where p is 1, 2 or 3, andwhere m is (4-p); and(ii) drying the
substrate.

45. The process of claim 45 wherein n is 4, p is 3, m is 1, and the
synthetic clay is a hectorite clay.

46. The process of claim 44 or 45 wherein the fluoroalkylsilyl moieties
are covalently bonded to the nanoparticle surface.

47. The process of claim 44 or 45 wherein the fluoroalkylsilyl surface
modified nanoparticles are formed at a concentration in the range of from
about 0.01% to about 50% by weight of the aqueous dispersion.

48. The process of claim 44 or 45 wherein the fluoroalkylsilane surface
modified nanoparticles are formed at a concentration in the range of from
about 1% to about 40% by weight of the aqueous dispersion.

49. The process of claim 44 or 45 wherein the fluoroalkylsilane surface
modified nanoparticles are formed at a concentration in the range of from
about 1% to about 8% by weight of the aqueous dispersion.

50. The process of claim 44 or 45, wherein said aqueous dispersion further
comprises a fluorinated resin emulsion.

51. The process of claim 44 or 45, wherein said aqueous dispersion further
comprises an alkylated inorganic nanoparticle having no fluorine.

52. The process of claim 44 or 45, wherein said aqueous dispersion further
comprises at least one member selected from the group consisting of a
wetting agent, anti-soil agent, anti-stain agent, fluorochemical resin,
surfactant and mixtures thereof.

53. The process of claim 44 or 45, wherein said aqueous dispersion further
comprises a component moiety bonded to the surface of the nanoparticles
having the formula:[H(CH2)M]n--Si--(O--)p.where M is
an integer between 1 and 12,where p is 1, 2, or 3, andwhere n is 4-p.

54. The process of claim 44 or 45, wherein said substrate is selected from
the group consisting of synthetic fiber, natural fiber, stone, ceramic,
glass, plastic and composites.

55. A composition comprising:a surface modified nanoparticle comprising:
(1) a fluoroalkylsilyl having the following
formula:(F(CF2)nCH2CH2)mSi(O--)p,where n is
2, 3 or 4,where p is 1, 2 or 3, andwhere m is (4-p), and (2) a component
moiety having the formula:[H(CH2)M]nSi--(O--)p.where
M is an integer between 1 and 12,where p is 1, 2, or 3, andwhere n is
4-p; wherein the nanoparticle comprises at least one member selected from
the group consisting of silica, titania, zirconia, layered magnesium
silicate, aluminosilicate, natural clay, synthetic clay and mixtures
thereof.

56. A composition comprising:a fluoroalkylsilyl surface modified
nanoparticle, wherein the nanoparticle comprises at least one member
selected from the group consisting of titania, zirconia, layered
magnesium silicate, aluminosilicate, natural clay, synthetic clay and
mixtures thereof, and wherein the fluoroalkylsilyl
is:(F(CF2)nCH2CH2)mSi(O--)p,where n is 2, 3
or 4,where p is 1, 2 or 3,and where m is (4-p).

Description:

[0002]The invention relates to compositions of surface modified
nanoparticles which are effective in treating soft and hard substrates to
impart useful properties, including resistance to both water and oil. The
invention also relates to aqueous dispersions of the surface modified
nanoparticles, processes of making the composition and articles made with
the compositions.

BACKGROUND OF THE INVENTION

[0003]Many different compositions have been used, in varying degrees of
success, to treat surfaces, fabrics and fibers to impart improved
resistance to soil deposition and to exhibit water and oil repellency.
However, those involving volatile organic compounds with the potential to
be carried forward to the consumer are now to be avoided as much as
possible, especially in carpet manufacturing. Excessive amounts of
surfactant are also undesirable, because retention by treated substrates
such as carpet results in increased affinity for soiling.

[0004]Fluorochemical resin emulsions have been used to create low soiling
soft surfaces having water repellency as disclosed in U.S. Pat. No.
3,329,661. However, these materials are expensive and they are
environmentally persistent. Therefore there is a need to reduce the
overall usage of such compounds while retaining the highly valuable soil
resistance and water repellency attributes they provide. Unfortunately,
all of the conventional alternative compositions exhibit unsolved
problems.

[0005]U.S. Pat. No. 6,225,403 to Knowlton, hereby fully incorporated
herein, discloses the use of fabric surface treating compositions
comprised of a blend of fluorochemical resins with colloidal sol
dispersions of organosiloxane co-polymers. This blend allows for reduced
add-on levels of fluorochemicals on soft-surfaces to achieve acceptable
soil repellency. However, significant concentrations of fluorochemicals
are still required to achieve the desired anti-soiling and hydrophobic
effects and the apparent softness of treated articles can be adversely
affected.

[0006]The production of more hydrophobic materials than siloxane typically
involves fluorinated hydrocarbons, organic solvents and surfactants; and
solvents such as ethanol, methanol, isopropanol, chloroform, and acetone
are present as major components in both the creation and the
stabilization of materials of this kind, such as fluoroalkyl modified
silica particles. U.S. Pat. Nos. 5,801,092 and 6,045,962 disclose typical
examples of such synthesis and dispersion. Solvent removal tends to be
destabilizing to such dispersions, causing particles to precipitate or
agglomerate, and once aggregated it is very difficult to disperse them
effectively. Therefore the approaches described in the above disclosures
are not suitable for creating a stable aqueous dispersion of particles
without undesirably high concentrations of volatile organic solvents or
surfactants.

[0007]United States patent application 2005/0227077 to Sugiyama discloses
a process of making nanoparticles coated with cross-linked fluoropolymers
suitable for molding material applications involving sequential steps of
making fluoroalkylsilane modified silica in the presence of
fluorosurfactants and water followed by the addition of unsaturated
fluoropolymer monomers and polymerization into fluoropolymer coated
particles. Sugiyama teaches that substantial concentrations of surfactant
are required, both to disperse the inorganic particles prior to
fluoroalkylation and to direct fluoropolymer monomers onto the silica
particle surface. Fluorosurfactants are preferred, and concentrations
higher than 10-20% of the weight of the reactant inorganic particles are
deemed effective. Unfortunately, as indicated above, the high cost and
environmental concerns related to fluorosurfactants make, the approach
taught by Sugiyama unsuitable for application to manufacturing processes
such as carpet fabric treatment.

[0008]U.S. Pat. No. 7,037,591 (Henze et al.) and United States patent
application 20060292345 disclose another approach to create disperse
hydrophobic siliceous nanoparticles which utilizes the sol-gel process
wherein a silicate sol-gel precursor and a fluoroalkylsilane (FAS)
reagent are mixed and co-condensed to produce particles. This approach is
not favored where substantial quantities of material are involved because
many of the expensive fluoroalkyl groups are incorporated into the
particle structure and not presented to the surface of the nanoparticle
where they can create a useful effect. Furthermore, the sol-gel
co-condensation synthetic route still utilizes organic solvents with the
same detrimental effects as outlined above.

SUMMARY OF THE INVENTION

[0009]Therefore, a need exists for an improved composition for treating
soft and hard substrates to impart softness and/or hydrophobic behavior,
including soil and oil resistance. To that end, an improved surface
modified fluoroalkylated nanoparticle is desired, wherein the fluoroalkyl
groups are presented to the surface of the nanoparticle to create a
useful hydrophobic effect and wherein both surfactants and volatile
organic solvents are substantially absent from the composition to be
applied to the substrate.

[0010]In accordance with one aspect of the disclosed composition, it has
now been found that certain novel compositions can be produced comprising
inorganic nanoparticles which have been surface modified via bi-phasic
reaction with liquid fluoroalkylsilane (FAS) reagents in aqueous media.
Aqueous dispersions of the disclosed composition are monophasic,
optically transparent and stable without significant aggregation or
precipitation and with little or no additional solvents or surfactants.
The composition comprises: an aqueous dispersion of fluoroalkylsilyl
surface modified nanoparticles, wherein the nanoparticles comprise at
least one member selected from the group consisting of silica, titania,
zirconia, layered magnesium silicate, aluminosilicate, natural clay,
synthetic clay and mixtures thereof, and wherein the fluoroalkylsilyl is:
(F(CF2)nCH2CH2)mSi(O--)p, where n is 2, 3
or 4, p is 1, 2 or 3, and m is (4-p). Also, the composition can further
comprise an additional component moiety bonded to the surface of the
nanoparticle having the formula:
[H(CH2)m]nSi--(O--)p, where M is an integer between 1
and 12, p is 1, 2, or 3, and n is 4-p. The additional component can be
methylsilyl. Further, articles comprising the fluoroalkylsilyl surface
modified nanoparticle are disclosed. The article can include fabrics,
carpets, or paper. The article exhibits improved resistance to soil
deposition, and both water and oil repellency.

[0011]In accordance with another aspect, a process of making an aqueous
dispersion of fluoroaklysilyl surface modified nanoparticles is
disclosed. The process comprises: (i) creating an aqueous dispersion of
at least one member selected from the group consisting of silica,
titania, zirconia, layered magnesium silicate, aluminosilicate, natural
clay, synthetic clay and mixtures thereof; (ii) adding a water immiscible
fluoroalkylsilane reagent to the aqueous dispersion to form a
heterogeneous mixture where the fluoroalkylsilane reagent is:
(F(CF2)nCH2CH2)mSi(O--R)p, where n is 2, 3
or 4, where p is 1, 2 or 3, where m is (4-p), and where R is selected
from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl,
isobutyl, and --C(O)CH3; and (iii) mixing the heterogeneous mixture
until it becomes a homogeneous aqueous dispersion of fluoroalkysilyl
surface modified nanoparticles. Additionally, a component having the
formula: [H(CH2)m]n--Si--(X)p, where M is an integer
between 1 and 12, p is 1, 2, or 3, n is 4-p, and where X is selected from
the group consisting of methoxy, ethoxy, propoxy, butoxy, acetoxy, and
chloride leaving groups, can be added prior to the addition of the
fluoroalkylsilane.

[0012]In yet another aspect, a modified substrate is disclosed. The
modified substrate comprises a fluoroalkylsilyl surface modified
nanoparticle on at least one surface of the substrate, wherein the
nanoparticle comprises at least one member selected from the group
consisting of titania, zirconia, layered magnesium silicate,
aluminosilicate, natural clay, synthetic clay and mixtures thereof, and
wherein the fluoroalkylsilyl is
(F(CF2)nCH2CH2)n--Si(O--)p, where n is 2, 3
or 4, where p is 1, 2 or 3, and where m is (4-p). The substrate can
further comprise an additional component moiety bonded to the surface of
the nanoparticle having the formula:
[H(CH2)M]n--Si--(O--)p, where M is an integer between
1 and 12, p is 1, 2, or 3, and n is 4-p. When the substrate comprises the
additional component moiety, the nanoparticle can be selected from the
group consisting of silica, zirconia, titania, layered magnesium
silicate, aluminosilicate, natural clay, synthetic clay and mixtures
thereof. The substrate can be synthetic fiber, natural fiber, stone,
ceramic, glass, plastic, and composites. Further, articles can be made
from the substrates, including carpets, paper, and fabrics made from
synthetic and natural fiber. The substrates and articles exhibit improved
resistance to soil deposition, and both water and oil repellency.

[0013]In a further aspect, a process of making a substrate that is
hydrophobic and soil resistant is disclosed. The process comprises (i)
applying an aqueous dispersion of fluoroalkylsilyl surface modified
nanoparticles to a substrate, wherein said aqueous dispersion comprises
at least one member selected from the group consisting of silica,
titania, zirconia, layered magnesium silicate, aluminosilicate, natural
clay, synthetic clay and mixtures; and wherein said fluoroalkylsilyl is:
(F(CF2)nCH2CH2)mSi(O--)p, where n is 2, 3
or 4, where p is 1, 2 or 3, and where m is (4-p); and (ii) drying the
substrate. The aqueous dispersion of fluoroalkylsilyl surface modified
nanoparticles can also comprise an additional component moiety bonded to
the surface of the nanoparticle having the formula:
[H(CH2)m]nSi--(O--)p, where M is an integer between 1
and 12, p is 1, 2, or 3, and n is 4-p. The substrate can be synthetic
fiber, natural fiber, stone, ceramic, glass, plastic, and composites.

[0014]In yet a further aspect, a composition comprising a surface modified
nanoparticle is disclosed. The surface modified nanoparticle comprises a
fluoroalkylsilyl having the formula:
(F(CF2)nCH2CH2)mSi(O--)p, where n is 2, 3
or 4, where p is 1, 2 or 3, and where m is (4-p), wherein the
nanoparticle is selected from the group consisting of zirconia, titania,
layered magnesium silicate, aluminosilicate, natural clay, synthetic clay
and mixtures thereof. The surface modified nanoparticle can optionally
comprise an additional component moiety having the formula:
[H(CH2)M]n--Si--(O--)p, where M is an integer between
1 and 12, p is 1, 2, or 3, and n is 4-p. When the surface modified
nanoparticle comprises the additional component moiety, the nanoparticle
can be selected from the group consisting of silica, zirconia, titania,
layered magnesium silicate, aluminosilicate, natural clay, synthetic clay
and mixtures thereof.

DETAILED DESCRIPTION OF THE INVENTION

[0015]A composition for treating soft and hard substrates to impart
softness and/or hydrophobic behavior, including soil and oil resistance
is disclosed. The composition comprises a fluoroalkylated nanoparticle
modified at the surface by reaction in water with a specific
fluoroalkylsilane (FAS) reagent that is suited to conducting such a
reaction efficiently in aqueous media. More specifically, the composition
can comprise an aqueous dispersion of fluoroalkylsilyl surface modified
nanoparticle, wherein the nanoparticle comprises at least one member
selected from the group consisting of silica, titania, zirconia, layered
magnesium silicate, aluminosilicate, natural clay, synthetic clay and
mixtures thereof, and wherein the fluoroalkylsilyl is:
(F(CF2)nCH2CH2)mSi(O--)p, where n is 2, 3
or 4, p is 1, 2 or 3, and m is (4-p), including:
(F(CF2)nCH2CH2)mSi(O--)p, where n can be 4,
p can be 3 when m is 1. The nanoparticle can comprise silica, titania,
zirconia, layered magnesium silicates, aluminosilicates, clays and
mixtures thereof; including a synthetic hectorite clay. A mixture can be
synthetic hectorite clay and silica. The fluoroalkylsilyl moieties can be
covalently bonded to the nanoparticle surface. This composition is formed
by reaction of a water immiscible specific fluoroalkylsilane reagent
emulsified in water with preformed inorganic nanoparticles dispersed in
the aquaeous phase such that the fluoroalkylsilane reagent is covalently
bonded to the nanoparticles predominantly at the particle surface as
described in process above. This dispersion composition can then be
applied to a substrate. The composition can optionally comprise a
component moiety bonded to the surface of the nanoparticle having the
formula: [H(CH2)M]n--Si--(O--)p, where M is an
integer between 1 and 12, p is 1, 2, or 3, and n is 4-p. The optional
component can be methylsilyl.

[0016]The nanoparticle can comprise silica, titania, zirconia, layered
magnesium silicates, aluminosilicates, clays and mixtures thereof, for
example the clay can be a synthetic hectorite clay, for example a mixture
can be synthetic hectorite clay and silica. The fluoroalkylsilyl
molecules can be covalently bonded to the nanoparticle surface.

[0017]The fluoroalkylsilyl surface modified nanoparticles can be present
at a concentration in the range of from about 0.01% to about 50% by
weight of the total composition of the dispersion, for example in the
range of from about 1% to about 40% by weight, including about 1% to
about 8% by weight of the total composition. Stable aqueous dispersions
of fluoroalkylsilyl surface modified nanoparticles wherein the
nanoparticles are synthetic hectorite clay can be formed at a
concentration in the range of from about 0.01% to about 12% by weight of
the total composition, including about 1% to about 8% by weight of the
total composition. Depending on the final use and the substrate to be
treated, the dispersion of the present invention can be diluted for more
efficient application or to control the level of moisture imparted in the
treatment process. Again, depending on the nature of the substrate that
is to be treated, its intended use and the process of manufacture, other
chemistries as may be known in the art can be combined with the aqueous
dispersion of the instant invention at suitable concentration ranges

[0018]The composition can further comprise a fluorinated resin emulsion,
an alkylated inorganic nanoparticle having no fluorine and/or at least
one member selected from the group consisting of a wetting agent,
anti-soil agent, fluorochemical resin, surfactant and mixtures thereof.

[0019]Optionally, the composition can be blended with additional wetting
agents, anti-soil agents, fluorochemical resins, surfactants or mixtures
thereof, as known in the art, in order to simplify the manufacturing
process at hand. While the aqueous dispersion is generally compatible, it
is naturally desirable to avoid the addition of materials that would
coalesce or precipitate the nanoparticles or otherwise diminish efficacy
or utility.

[0020]The disclosed dispersions are surprisingly stable and exist
indefinitely at moderately high concentrations as transparent aqueous
mixtures in spite of the intrinsically hydrophobic nature of
fluoroalkylated surfaces.

[0021]The compositions can be useful to treat soft surfaces to impart
several valuable attributes. Hard surfaces, fabrics and fibers treated
with the various dispersions described have also been shown to have
increased resistance to soil deposition and to exhibit water and oil
repellency

[0022]A process for making a fluoroaklysilyl surface modified nanoparticle
is also disclosed. The process comprises: (i) creating an aqueous
dispersion of at least one member selected from the group consisting of
silica, titania, zirconia, layered magnesium silicate, aluminosilicate,
natural clay, synthetic clay and mixtures thereof; (ii) adding a water
immiscible fluoroalkylsilane reagent to the aqueous dispersion to form a
heterogeneous mixture where the fluoroalkylsilane reagent is:
(F(CF2)nCH2CH2)mSi(O--R)p, where n is 2, 3
or 4, p is 1, 2 or 3, m is (4-p), and R is selected from the group
consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and
--C(O)CH3; and (iii) mixing the heterogeneous mixture until it
becomes a homogeneous aqueous dispersion of fluoroalkylsilane surface
modified nanoparticles. The fluoroalkylsilane is:
(F(CF2)nCH2CH2)mSi(O--R)p, where n can be
4, p can be 3 when m is 1 and R can be selected from the group consisting
of methyl and ethyl. The nanoparticle can comprise silica, titania,
zirconia, layered magnesium silicates, aluminosilicates, clays and
mixtures thereof, for example the clay can be a synthetic hectorite clay,
for example a mixture can be synthetic hectorite clay and silica. The
fluoroalkylsilane molecules can be covalently bonded to the nanoparticle
surface, creating a fluoroalkylsilyl moiety. The fluoroalkylsilyl surface
modified nanoparticles can be formed at a concentration in the range of
from about 0.01% to about 50% by weight of the total composition, for
example from about 1% to about 40% by weight of the total composition or
from about 1% to about 8% by weight of the total composition. The process
can further comprise adding a fluorinated resin emulsion prior applying
the aqueous dispersion. Additionally, the process can further comprise
adding an alkylated inorganic nanoparticle having no fluorine prior
applying the aqueous dispersion. Moreover, the process can further
comprise adding at least one member selected from the group consisting of
a wetting agent, anti-soil agent, fluorochemical resin, surfactant and
mixtures thereof prior applying the aqueous dispersion. Optionally, a
compound having the formula: [H(CH2)M]n--Si--(X)p,
where M is an integer between 1 and 12, p is 1, 2, or 3, n is 4-p, and
where X is selected from the group consisting of methoxy, ethoxy,
propoxy, butoxy, acetoxy, and chloride leaving groups, can be added prior
to the addition of the fluoroalkylsilane. A recirculation pump and static
mixer may be used in the disclosed process to further increase the
interfacial contact between the immiscible fluoroalkylsilane and
nanoparticles.

[0023]The fluoroalkylsilane reactant used in step (ii) of the process to
create the fluoroalkylsilyl surface modified nanoparticles is:
(F(CF2)nCH2CH2)mSi(O--R)p, where n is 2, 3
or 4; where p is 1, 2 or 3; where (m+p)=4; and where R is selected from
the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl,
isobutyl, and --C(O)CH3. The fluoroalkyl moiety of the alkylsilane
reactant can be a perfluoroalkane of two to four carbons in length, for
example a four carbon nanofluoroalkane (n is 4), where m is 1 and p is 3,
and where R is either methyl or ethyl. Extended perfluoroalkane chains
can be used to achieve greater degrees of hydrophobicity in treated
substrates. However, FAS reagents having perfluoroalkane chains longer
than four carbon atoms (n value greater than 4) are not suitable for
making the disclosed aqueous dispersions and that the addition of
undesirable levels of solvents or surfactants would be required to
stabilize both reactants and product dispersions in the disclosed
process.

[0024]In one aspect of the disclosed process,
1,1,2,2-tetrahydro-nonafluorohexyl trimethoxysilane can be added slowly
with stirring to a 25% (w/w) aqueous dispersion of colloidal silica (20
nm particles) with pH 9 to form a liquid-liquid emulsion of cloudy
appearance. Optionally, a recirculation pump and static mixer can be used
with or without the mechanical stirrer to increase interfacial contact of
the FAS with the colloidal silica. The FAS minor liquid phase is consumed
with stirring over a period of hours gradually reducing to a single
liquid phase dispersion that remains stable in the absence of stirring.
The resulting stable aqueous dispersion contains dispersed silica
nanoparticles that have a covalently bonded hydrophobic layer on the
particle surface.

[0025]In another aspect of the disclosed process,
1,1,2,2-tetrahydro-nonafluorohexyl trimethoxysilane can be added slowly
to a 5% (w/w) aqueous dispersion of synthetic hectorite clay
nanoparticles sold by the trade name Laponite® RDS from Rockwood
Additives Ltd. The aqueous hectorite clay dispersion is natively above pH
9 and slow addition of the FAS with high stir rate forms a liquid-liquid
emulsion of cloudy appearance. Optionally, a recirculation pump and
static mixer can be used with or without the mechanical stirrer to
increase interfacial contact of the FAS with the hectorite clay. The FAS
minor liquid phase is consumed with stirring over a period of hours
gradually reducing to a single liquid phase dispersion that remains
stable in the absence of stirring. Optionally, the dispersion of the
present invention can be blended with fluorinated resin emulsions or with
dispersions of alkylated inorganic nanoparticles having no fluorine. For
example, the dispersions of the fluoroalkyl modified clay nanoparticles
described above can be blended with an aqueous dispersion of colloidal
silica nanoparticles which have been surface modified with
methyltrimethyoxysilane (MTMS) so that the resulting aqueous dispersion
comprises two distinctly different nanoparticles.

[0026]Also disclosed are substrates and processes for making the same
using the fluoroalkylsilyl surface modified nanoparticles. The substrate
comprises: a fluoroalkylsilyl surface modified nanoparticle on at least
one surface, wherein the nanoparticle comprises at least one member
selected from the group consisting of titania, zirconia, layered
magnesium silicate, aluminosilicate, natural clay, synthetic clay and
mixtures thereof, and wherein the fluoroalkylsilyl is:
(F(CF2)nCH2CH2)mSi(O--)p, where n is 2, 3
or 4, p is 1, 2 or 3, and m is (4-p). The nanoparticle of the present
invention can comprise titania, zirconia, layered magnesium silicates,
aluminosilicates, clays and mixtures thereof, for example the clay can be
a synthetic hectorite clay, for example a mixture can be synthetic
hectorite clay and zirconia. The substrate can be selected from the group
consisting of synthetic fiber, natural fiber, stone, ceramic, glass,
plastic and composites. The fluoroalkylsilyl can also include:
(F(CF2)nCH2CH2)mSi(O--)p, where n can be 4,
p can be 3 when m is 1. The fluoroalkylsilyl can be covalently bonded to
the nanoparticle surface. The substrate can have pores having an average
diameter in the range of from about 100 to about 100,000 nanometers. The
fluoroalkylsilane surface modified nanoparticle can form at least one
layered structure on the substrate, wherein the layered structure has a
thickness of about 10,000 nanometers or less, and a width and length of
about 100,000 nanometers or more. The substrate can optionally comprise a
component moiety bonded to the surface of the nanoparticle having the
formula: [H(CH2)m]nSi--(O--)p, where M is an integer
between 1 and 12, p is 1, 2, or 3, and n is 4-p. When the nanoparticle
comprises the optional component moiety, the nanoparticle can include
silica, titania, zirconia, layered magnesium silicates, aluminosilicates,
clays and mixtures thereof.

[0027]The substrate can be a polyamide fiber wherein the composition
imparts dry soil, water, and oil repellency with lower levels of
elemental fluorine used compared with coatings of traditional
fluorochemical resin emulsions. Soft substrates coated with the present
invention have been found to exhibit superior water repellency with less
elemental fluorine than found in coatings of traditional fluorochemical
resins. The substrate can also include synthetic fiber, natural fiber,
stone, ceramic, glass, plastic and composites.

[0028]The process of making the substrate with the aqueous dispersion of
nanoparticles comprises applying the aqueous dispersion of
fluororalkylsilyl surface modified nanoparticles to a substrate; and
drying the substrate.

[0029]Also disclosed are articles made from substrates comprising the
fluoroalkylsilyl surface modified nanoparticles. More specifically, an
article comprises a composition comprising: a fluoroalkylsilyl surface
modified nanoparticle, wherein the nanoparticle comprises at least one
member selected from the group consisting of titania, zirconia, layered
magnesium silicate, aluminosilicate, natural clay, synthetic clay and
mixtures thereof, and wherein the fluoroalkylsilyl is:
(F(CF2)nCH2CH2)mSi(O--)p, where n is 2, 3
or 4, p is 1, 2 or 3, and m is (4-p), and optionally a component moiety
bonded to the surface of the nanoparticle having the formula:
[H(CH2)m]n--Si--(O--)p, where M is an integer between
1 and 12, p is 1, 2, or 3, and n is 4-p. Articles can include but are not
limited to fabrics, rugs, carpets, paper, stone, and finished or painted
surfaces, for example fabric, carpet or paper, more particularly a fabric
or a carpet. When the article is a fabric or carpet, or includes the
optional component moiety, the nanoparticles can also include silica. For
a fabric or a carpet, the total concentration of fluorine is in a range
of from about 10 ppm to about 500 ppm w/w of exposed substrate, including
about 50 ppm to about 300 ppm w/w of exposed substrate. For a fabric or a
carpet, the substrate retains the fluoroalkylsilyl surface modified
nanoparticle at a weight in the range of from about 0.01% to about 2.0%
by weight of the exposed substrate, including from about 0.1% to about
1.0% by weight of the exposed substrate; or wherein the substrate retains
elemental fluorine in the range of from about 0.0001% to about 0.10% by
weight of the exposed substrate, including from about 0.0001% to about
0.010% by weight of the exposed substrate. For a fabric or a carpet, the
substrate retains fluoroalkylsilyl surface modified nanoparticles in the
range of from about 0.01 to about 3 grams per square meter of surface
area, including from about 0.1 to about 2 grams per square meter of
surface area. For carpets or fabrics, the aqueous dispersion can be
applied from about 5 ounces per square yard of carpet or fabric to about
150 ounces per square yard of carpet or fabric.

DEFINITIONS

[0030]Nanoparticle is defined as a multidimensional particle in which one
of its dimensions is less than 100 nm in length.

[0031]FAS means the class of fluoroalkylsilane reagents used to impart
fluorinated organic functionality including, but not limited to, the
inorganic particles of this invention. FAS reagents specifically include,
but are not limited to structures of the formula:
(F(CF2)nCH2CH2)mSi(OR)p where n is 2, 3 or
4; where p is at least 1; where m is at least 1; where m+p=4; and where R
is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or
--C(O)CH3. Although less preferred for the process of making here
disclosed, other structures having perflourinated alkyl terminal
functionality should also be understood as being contemplated by this
disclosure. FAS reagents can also include structures of the formula:
(F(CF2)nCH2CH2)mSi(X)p where n is 2, 3 or
4; where p is at least 1; where m is at least 1; where m+p=4; and where X
is a halogen such as chlorine, bromine or iodine. FAS reagents can also
include structures of the formula:
(F(CF2)nCH2CH2)mSiR'p (X) where n>2, and
m+p=3, R' is methyl or ethyl bonded to the silicon atom and where X is a
halogen such as chlorine, bromine or iodine that is bonded to the silicon
atom.

[0032]Clay particles can refer to particles substantially comprising
minerals of the following geological classes: smectites, kaolins,
illites, chlorites, and attapulgites. These classes include specific
clays such as montmorillonite, bentonite, pyrophyllite, hectorite,
saponite, sauconite, nontronite, talc, beidellite, volchonskoite,
vermiculite, kaolinite, dickite, antigorite, anauxite, indellite,
chrysotile, bravaisite, suscovite, paragonite, biotite, corrensite,
penninite, donbassite, sudoite, pennine, sepiolite, and polygorskyte. The
clay minerals of the invention may be either synthetic or natural and are
exfoliated to be capable of forming aqueous micro dispersions. An example
of one embodiment of the present invention uses synthetic hectorite clay
nanoparticles sold by the trade name Laponite® from Rockwood
Additives Ltd. Preferred embodiments of the present invention use
Laponite RDS®, Laponite JS®, and Laponite RD®.

[0033]An aqueous dispersion means a colloidal dispersion, which is a
system of finely divided particles of small size, such as nanoparticles,
which are uniformly dispersed in a manner such that they are not easily
filtered or gravitationally separated.

[0034]An aqueous micro dispersion is defined as a dispersion of particles
predominately having at least one dimension that is less than about 100
nm in extent.

[0035]A non-solubilized aqueous micro dispersion is an aqueous micro
dispersion that is stable for extended periods of time (two or more
months) without water compatible surfactants.

[0036]OWF is weight per weight of fiber.

[0037]WPU (wet pick up) is the fraction of the weight of fabric added in
liquid form in treating a fibrous substrate (w/w). For carpet, the weight
of fabric is considered the carpet fiber face weight.

[0038]Layered structure is where overlap of nanoparticles is observed, and
where flat layers or sheets are observed rather than round, globular or
clumped aggregate structures.

[0039]Test Methods

[0040]Drum soiling procedure was followed as closely as possible from ASTM
D6540

EXAMPLES

[0041]Aqueous Micro Dispersion Preparatory Example 1: To a 250 mL round
bottom flask was added 59.6 grams of 40% anionic colloidal silica
(LUDOX® AS-40, from W.R. Grace) and 40.0 grams of de-ionized water
with stirring to form a liquid-liquid emulsion of cloudy appearance. The
pH of the resulting aqueous colloidal silica dispersion was between 9 and
10. The dispersion was stirred at 32° C. under nitrogen and 1.798
mL of 1,1,2,2-tetrahydro-nonafluorohexyl trimethoxysilane (density=1.335
g/mL, from Gelest) was added over 225 minutes via syringe and syringe
pump. After stirring for 20 hrs at 32° C. the mixture was observed
to be a single liquid phase and was then allowed to cool to RT and a
clear aqueous dispersion was produced. The product was filtered through 1
micron glass-fiber filter paper and the final concentration of the
dispersion was essentially unchanged as only a very slight film of
precipitate was observed on the filtration media.

[0042]Aqueous Micro Dispersion Preparatory Example 2: To a 500 mL round
bottom flask was added 190 grams of de-ionized water and the temperature
was brought to 38 deg C. with rapid stirring. 10.00 gram of Laponite®
RDS clay powder (from Rockwood Additives) was added slowly over 15
minutes in small increments and then stirred for 1 hr at 38° C.,
creating a clear aqueous dispersion with a pH of between 9 and 10. The
temperature of the Laponite® RDS dispersion was brought to 32°
C. while stirring under nitrogen and 2.757 mL of
1,1,2,2-tetrahydro-nonafluorohexyl trimethoxysilane (density=1.335 g/mL,
from Gelest) was added over 336 minutes via syringe and syringe pump with
stirring to form a liquid-liquid emulsion of cloudy appearance. After
addition, the dispersion was stirred for 35 hrs at 32° C. and was
observed to be a single liquid phase. It was then allowed to cool to RT
and a clear aqueous dispersion was produced. The product was filtered
through 1 micron glass-fiber filter paper and the final concentration of
the dispersion was essentially unchanged as only a very slight film of
precipitate was observed on the filtration media.

[0043]Aqueous Micro Dispersion Preparatory Example 3: To a 3000 mL round
bottom flask with 3 necks and equipped with overhead stirrer was added
596 grams of 40% anionic colloidal silica (LUDOX® AS-40, from W.R.
Grace) and 396 grams of de-ionized water at room temperature with
stirring. The pH of the resulting aqueous dispersion was between 9 and
10. The dispersion was brought to 30° C. and stirred under
nitrogen, and 13.20 mL of methyl trimethoxysilane (density=0.955 g/mL,
from Aldrich) was subsequently added over 127 minutes via syringe and
syringe pump. After stirring for 1 hr at 30° C. it was allowed to
cool to RT and a clear aqueous dispersion was produced. The product was
filtered through 1 micron glass-fiber filter paper and the final
concentration of the dispersion was essentially unchanged at
approximately 25% w/w solids, as only a very slight film of precipitate
was observed on the filtration media.

[0044]Aqueous Micro Dispersion Preparatory Example 4: To a small beaker
was added 59.6 grams of 40% anionic colloidal silica (LUDOX® AS-40
from W.R. Grace) and 40.4 grams of de-ionized water at room temperature
with stirring, to produce a solution with 25% solids. 0.744 ml of
methyltrimethylsiloxane (MTMS) was dripped into the stirring beaker using
a syringe pump set to deliver 0.01 ml/min. Approximately 135 minutes
after addition of MTMS (i.e. about 1 hour after it ended), the FAS
addition started. 0.360 ml of FAS was added at 0.01 ml/min, using a 1 ml
glass Hamilton gas-tight syringe. The beaker was covered in parafilm and
stirred at 1200 rpm for approximately 48 hours. During the 48 hour
stirring, a sludge formed that trapped the stir bar. No oil droplets were
visible on the top of the liquid surface. The product was filtered
through GFA paper, whereby 97 grams of product was collected.

[0045]Aqueous Micro Dispersion Preparatory Example 5: In a 15 liter
reactor, 2380 grams of deionized water and 3580 grams of 40% anionic
colloidal silica (LUDOX® AS-40 from W.R. Grace) was added to produce
a solution with 25% solids. In addition to mechanical stirring, the
reactor was fitted with a recirculating pump and tubing drawing the
solution through the pump and then through a static mixer tube and then
back to the reactor. 24.5 grams of MTMS was added dropwise to the
solution over minutes. The solution was allowed to mix for 1 hour. 66.45
grams of FAS was slowly added via glass funnel over 1.5 hours. After 4
hours of mixing, most of the FAS oily phase had disappeared from the
water surface indicating a single phase and that the FAS had reacted with
the particles. The solution was allowed to stand overnight and was
filtered through GFA glass filer paper. Approximately 12 grams of
unreacted byproduct was collected. The resulting aqueous dispersion was
stable and homogeneous. Upon allowing drops of the dispersion to
evaporate on the surface, a surprising hydrophobic film is formed, which
is substantially more hydrophobic than comparable amounts of fluorine
from Capstone® RCP (DuPont) or from a treated Ludox® with 100%
FAS monolayer (Preparatory Example 1).

[0046]Substrate Treatment Example 1: The stable aqueous dispersion from
Preparatory Example 1 was diluted with 82.4 grams of water and the
resulting solution sprayed on 46 ounce cut-pile carpet at 5% WPU and
curing in 150° C. oven for 6 min resulted in the OWF totals for
particle solids and fluorine as listed in Table 1. The results of the dry
soiling test (ASTM D6540) are also provided therein.

[0047]Substrate Treatment Examples 2: 58.8 grams of the stable aqueous
dispersion from Preparatory Example 2 was blended with 7.9 grams of the
aqueous dispersion from Preparatory Example 3 and then diluted with 33.3
grams of water at room temperature and the resulting solution sprayed on
46 ounce cut-pile carpet at 4.9% WPU. Drying in a 150° C. oven for
6 min gave ppm OWF totals for particle solids and fluorine listed in
Table 1. The results of the dry soiling test (ASTM D6540) are also
provided therein.

[0048]Substrate Treatment Example 3: 57.6 grams of the stable aqueous
dispersion from Preparatory Example 2 was blended with 1.2 grams of the
aqueous dispersion from Preparatory Example 3 and then diluted with 41.2
grams of DI water at room temperature and the resulting solution was
sprayed on 46 ounce cut-pile carpet at 4.9% WPU. Drying in a 150°
C. oven for 6 min gave ppm OWF totals for particle solids and fluorine
listed in Table 1. The results of the dry soiling test (ASTM D6540) are
also provided therein.

[0049]Substrate Treatment Example 4: 39.6 grams of the stable aqueous
dispersion from Preparatory Example 2 was blended with 4.0 grams of the
aqueous dispersion from Preparatory Example 3 and then diluted with 56.4
grams of DI water at room temperature and the resulting solution was
sprayed on 46 ounce cut-pile carpet at 4.9% WPU. Drying in a 150°
C. oven for 6 min gave ppm OWF totals for particle solids and fluorine
listed in Table 1. The results of the dry soiling test (ASTM D6540) are
also provided therein.

[0050]Substrate Treatment Example 5: 8.8 grams of the stable aqueous
dispersion from Preparatory Example 1 was blended with 4.8 grams of
CapstoneRCP (a commercial fluoro-resin aqueous emulsion from DuPont) and
then diluted with 86.4 grams of DI water at Room Temperature. The
resulting solution was sprayed on 46 ounce cut-pile carpet at 6.4% WPU.
Drying in a 150° C. oven for 6 min gave ppm OWF totals for
particle solids and fluorine listed in Table 1. The results of the dry
soiling test (ASTM D6540) are also provided therein.

[0051]Substrate Treatment Example 6: 7.9 grams of the stable aqueous
dispersion from Preparatory Example 1 was blended with 4.3 grams of the
aqueous dispersion from Preparatory Example 3 and then diluted with 87.8
grams of DI water at Room Temperature. The resulting solution was sprayed
on 46 ounce cut-pile carpet at 5.1% WPU. Drying in a 150° C. oven
for 6 min gave ppm OWF totals for particle solids and fluorine listed in
Table 1. The results of the dry soiling test (ASTM D6540) are also
provided therein.

[0052]Substrate Treatment Example 7: 0.8 grams of the stable aqueous
dispersion from Preparatory Example 4 was blended with 8.2 grams of 5801
stain resist from INVISTA North America S.a.r.l. The concentrated
solution was diluted with de-ionized water by a factor of 56.87 to obtain
a total solution weight equal to 250% of the fiber weight for the carpet
specimen to be treated. Diluted sulfamic acid was added to bring the pH
to 1.5. The bottle was inverted to mix thoroughly, and then the solution
was poured into a tray. The carpet was placed in the liquid with the
fiber facing down to soak it up. The carpet was rolled from one edge and
squeezed to disperse liquid. The carpet was placed back into the tray to
soak up any squeezed out liquid. The roll and squeeze technique was
repeated from the other three sides. The carpet was placed fiber facing
upwards on the conveyor belt of the steam table, with the steam valve
open part-way, the speed set to 10 (10 sec/1 inch), and the heater set to
100° C. After the carpet specimen passed through the oven, it was
sent through the steam/oven again with the fiber facing down. The steamed
carpet was rinsed in water, extracted with the vacuum of a Hot Water
Extraction device and air dried overnight. The treated specimen was
backed with duct tape and labeled prior to testing.

[0053]Substrate Treatment Example 8: 0.8 grams of the stable aqueous
dispersion from Preparatory Example 5 was blended with 0.36 grams of
Capstone RCP and 8.77 grams of 5801 stain resist from INVISTA North
America S.a.r.l. The concentrated solution was diluted with de-ionized
water by a factor of 54.8 to obtain a total solution weight equal to 250%
of the fiber weight for the carpet specimen to be treated. Diluted
Sulfamic Acid was added to bring the pH to 1.5. The bottle was inverted
to mix thoroughly, and then the solution was poured into a tray. The
carpet was placed in the liquid with the fiber facing down to soak it up.
The carpet was rolled from one edge and squeezed to disperse liquid. The
carpet was placed back into the tray to soak up any squeezed out liquid.
The roll and squeeze technique was repeated from the other three sides.
The carpet was placed fiber facing upwards on the conveyor belt of the
steam table, with the steam valve open part-way, the speed set to 10 (10
sec/1 inch), and the heater set to 100° C. After the carpet
specimen passed through the oven, it was sent through the steam/oven
again with the fiber facing down. The steamed carpet was rinsed in water,
extracted with the vacuum of a Hot Water Extraction device and air dried
overnight. The treated specimen was backed with duct tape and labeled
prior to testing.

[0054]Substrate Treatment Example 9: 2.0 grams of the stable aqueous
dispersion from Preparatory Example 5 was blended with 8.0 grams of 5801
stain resist. The concentrated solution was diluted with de-ionized water
by a factor of 50 to obtain a total solution weight equal to 250% of the
fiber weight for the carpet specimen to be treated. Diluted Sulfamic Acid
was added to bring the pH to 1.5. The bottle was inverted to mix
thoroughly, and then the solution was poured into a tray. The carpet was
placed in the liquid with the fiber facing down to soak it up. The carpet
was rolled from

[0055]one edge and squeezed to disperse liquid. The carpet was placed back
into the tray to soak up any squeezed out liquid. The roll and squeeze
technique was repeated from the other three sides. The carpet was placed
fiber facing upwards on the conveyor belt of the steam table, with the
steam valve open part-way, the speed set to 10 (10 sec/1 inch), and the
heater set to 100° C. After the carpet specimen passed through the
oven, it was sent through the steam/oven again with the fiber facing
down. The steamed carpet was rinsed in water, extracted with the vacuum
of a Hot Water Extraction device and air dried overnight. The treated
specimen was backed with duct tape and labeled prior to testing.

Comparative Example 1

[0056]As an industry standard benchmark for residential carpet anti-soil
treatments, 13.3 grams of Capstone® RCP solution (a commercial
fluoro-resin aqueous emulsion from DuPont) was diluted with 86.7 grams of
water and the resulting solution was sprayed on 46 ounce cut-pile carpet
at 9.2% WPU and curing in 150° C. oven for 6 min gave 610 ppm
fluorine OWF. Table 1 indicates the results of the dry soiling test (ASTM
D6540) for comparison to embodiments of the inventive examples.